Catalyst shuttling enabled by a thermoresponsive polymeric ligand: facilitating efficient cross-couplings with continuously recyclable ppm levels of palladium

Wang, Erfei; Chen, Mao

doi:10.1039/c9sc02171j

Cited by 12 publications

(6 citation statements)

References 66 publications

(94 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…With the same synthetic route, the WePhos 5000 4 b and PPh 3 ‐PEG 5000 4 c were prepared at 83 % and 87 % overall yields, respectively. The structures of 4 b and 4 c were also confirmed by MALDI‐TOF mass spectra (Figures S2c–S2d), NMR spectra and other measurements.…”

Section: Resultsmentioning

confidence: 99%

“…Recently, we demostrated a highly efficient and lowcatalyst-loading Pd-catalyzed SuzukiÀ Miyaura cross-coupling method with a polymeric monophosphine ligand, "WePhos", enabling rapid catalsyt shuttling, simple catalyst seperation and continuous catalyst-recycling synthesis under biphasic conditions (Scheme 1). [16] However, when further efforts were taken to extend the application scope of WePhos in other C-C bond forming cross-couplings, lower reactivities were observed, even at higher catalyst loadings. In this work, inspired by the elegent design of biaryldialkyl phosphine ligands, [17] we developed a poly(ethylene glycol) (PEG) linked ortho-MeOphenyldicyclohexylphosphine ligand, "MeO-WePhos", which allows extending the efficient shuttling catalysis to Pd-catalyzed cross-couplings inlcuding Sonogashira, Heck, Hiyama and Stille reactions as regulated by temperature.…”

Section: Introductionmentioning

confidence: 99%

“…Recently, we demostrated a highly efficient and low‐catalyst‐loading Pd‐catalyzed Suzuki−Miyaura cross‐coupling method with a polymeric monophosphine ligand, “WePhos”, enabling rapid catalsyt shuttling, simple catalyst seperation and continuous catalyst‐recycling synthesis under biphasic conditions (Scheme ) . However, when further efforts were taken to extend the application scope of WePhos in other C‐C bond forming cross‐couplings, lower reactivities were observed, even at higher catalyst loadings.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Shuttling Catalyst: Facilitating C−C Bond Formation via Cross‐Couplings with a Thermoresponsive Polymeric Ligand

Wang

Zhang

Zhong

et al. 2019

Israel Journal of Chemistry

Self Cite

View full text Add to dashboard Cite

A poly(ethylene glycol) (PEG) linked ortho-MeOphenyldicyclohexylphosphine (MeO-WePhos) ligand has been synthesized to promote Pd-catalyzed carbon-carbon bond formation by cross-couplings including Sonogashira, Heck, Hiyama and Stille reactions, providing corresponding (hetero)aryl substituted alkynes, alkenes and bi(hetero)aryls in good to excellent isolated yields with low Pd loadings. Facilitated by the lower critical solution temperature behaviour of the polymeric monophosphine ligand, the metalcomplex could rapidly shuttle between organic and water phases as regulated by temperature, enabling highly efficient catalyst recycling via a simple phase separation. The chemical structure of ligand was determined by matrixassisted laser desorption/ionization-time of flight mass spectrometry, nuclear magnetic resonance spectrometry and size-exclusion chromatography measurements. Notably, as demonstrated by the inductively coupled plasma-atomic emission spectrometry measurement, 98% Pd was kept in the water phase after 6 cycles of catalyst recycling experiments. Given the profound impact of transition-metalcatalyzed covalent bond formation and the increasing demand of sustainable chemistry, this work provides an alternative method to conduct cross-couplings with a polymeric shuttling catalyst. Scheme 5. Hiyama and Stille reaction with MeO-WePhos 5000 4 a. Conditions: 23 (0.5 mmol), 24 (0.6 mmol), K 2 CO 3 (1.0 mmol), water (0.8 mL), toluene (0.2 mL), 90°C, 6 h. Isolated yields are based on aryl bromides 23.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Shuttling Catalyst: Facilitating C−C Bond Formation via Cross‐Couplings with a Thermoresponsive Polymeric Ligand

Wang

Zhang

Zhong

et al. 2019

Israel Journal of Chemistry

Self Cite

View full text Add to dashboard Cite

show abstract

“…[ 211 ] Yang et al. [ 212 ] reported graphene oxide coated tunable magnetic nanorods for effective hyperthermia in mice models. Among the three different nanorods used, 460, 350, and 250 nm, the 350 nm nanorods have the highest SAR value of 1045 W g ‐1 at 0.2 mg mL ‐1 of Fe concentration.…”

Section: Biomedical Applications Of Mnpsmentioning

confidence: 99%

“…The 350 nm nanorods exhibited sufficient tumor volume reduction in the mice model and exhibited good biocompatibility in the MTT assay. [ 212 ]…”

Section: Biomedical Applications Of Mnpsmentioning

confidence: 99%

Recent progress of magnetic nanoparticles in biomedical applications: A review

et al. 2021

View full text Add to dashboard Cite

Magnetic nanoparticles (MNPs) offer tremendous potentialities in biomedical applications for a long while. Since these materials' interactions in biological media largely rely on their crystal structures, sizes, and shapes, detailed studies on their synthesis mechanism for medicinal aspects are crucial. Despite many review reports that have already been published on MNPs, they mainly have focused either on their perspective in biomedical applications or their synthesis and characterization along with functionalization mechanisms as individual entities. For this reason, this review uncovers a comprehensive insight into the ongoing improvement of fabrication processes, surface functionalization of MNPs for biomedical applications together. Besides, various magnetic nanocomposite (MNCs) for smart drug delivery, recent hyperthermia treatment, lab‐on‐a‐chip, and magnetic bio‐separation, and some of the recent emerging imaging techniques using MNPs are discussed. A detailed analysis of toxicity, challenges, and recent progress of clinical trials of MNPs is sketched out to open numerous entryways for advanced research on MNPs for biomedical applications.

show abstract

Palladium complexes of N,O‐bidentate ligands bearing N‐oxide units as simple and efficient catalysts for Suzuki–Miyaura reaction of aryl halides with arylboronic acids

Jia,

Huang

2024

Applied Organom Chemis

View full text Add to dashboard Cite

Palladium‐catalyzed Suzuki–Miyaura reaction is an important synthetic strategy for the synthesis of biaryl compounds. This work describes that palladium complexes with N,O‐bidentate ligands bearing N‐oxide units from cyclic secondary amines were used as highly efficient catalysts for Suzuki–Miyaura reactions of aryl halides with arylboronic acids. The reaction exhibited good functional group compatibility, high yields, and mild conditions. More importantly, these N,O‐coordinated palladium complexes could be easily prepared and displayed excellent catalytic performance for this classic Csp2–Csp2 coupling reaction in very short time.

show abstract

Catalyst shuttling enabled by a thermoresponsive polymeric ligand: facilitating efficient cross-couplings with continuously recyclable ppm levels of palladium

Abstract: A thermoresponsive polymeric Pd-complex was synthesized, enabling highly efficient cross-couplings and continuous catalyst-recycling flow reactions with ultralow Pd usages.

Cited by 12 publications

References 66 publications

Shuttling Catalyst: Facilitating C−C Bond Formation via Cross‐Couplings with a Thermoresponsive Polymeric Ligand

Shuttling Catalyst: Facilitating C−C Bond Formation via Cross‐Couplings with a Thermoresponsive Polymeric Ligand

Recent progress of magnetic nanoparticles in biomedical applications: A review

Palladium complexes of N,O‐bidentate ligands bearing N‐oxide units as simple and efficient catalysts for Suzuki–Miyaura reaction of aryl halides with arylboronic acids

Contact Info

Product

Resources

About